Metal-free dihydrogen activation chemistry: structural and dynamic features of intramolecular P/B pairs

被引：123

作者：

Spies, Patrick ^{[1
]}

Kehr, Gerald ^{[1
]}

Bergander, Klaus ^{[1
]}

Wibbeling, Birgit ^{[1
]}

Froehlich, Roland ^{[1
]}

Erker, Gerhard ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

DALTON TRANSACTIONS | 2009年 / 09期

关键词：

FREE CATALYTIC-HYDROGENATION; FRUSTRATED LEWIS PAIRS; DENSITY-FUNCTIONAL THEORY; HOMOGENEOUS HYDROGENATION; ENANTIOSELECTIVE REDUCTION; POLYCYCLIC ARENES; BORANE; PHOSPHINES; REACTIVITY; COMPLEXES;

D O I：

10.1039/b815832k

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Hydroboration of allyl(dimesityl) phosphane with HB(C6F5)(2) gives the intramolecular five-membered P-B Lewis pair 7, that was characterized by X-ray diffraction. Similarly, HB(C6F5)(2) addition to the substrates (mesityl)(2)P-CR=CH2(R=CH3, Ph) yield the corresponding (mesityl)(2)P(mu-CHRCH2) B(C6F5)(2) products 9a (R=CH3) and 9b (R=Ph) that show a weak intramolecular P... B interaction. The activation energy of the (reversible) P... B cleavage of these substrates was determined by dynamic F-19 NMR spectroscopy (9a: Delta G(inv)(not equal) (280 K) = 11.7 +/- 0.4 kcal mol(-1)). Compounds 9b and 9c show similar values. Compound 9c was prepared by HB(C6F5)(2) addition to (mesityl)(2)P-CH=CHSiMe3. Compound 9a reacts rapidly with dihydrogen (2.5 bar) at room temperature in pentane to give the zwitterionic H-2-activation product (mesityl)(2)PH+(mu-CHMeCH2)BH-(C6F5)(2)(11).

引用

页码：1534 / 1541

页数：8

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